EP0456823A1 - Resine a base de chlorure de vinyle - Google Patents

Resine a base de chlorure de vinyle Download PDF

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Publication number
EP0456823A1
EP0456823A1 EP90900332A EP90900332A EP0456823A1 EP 0456823 A1 EP0456823 A1 EP 0456823A1 EP 90900332 A EP90900332 A EP 90900332A EP 90900332 A EP90900332 A EP 90900332A EP 0456823 A1 EP0456823 A1 EP 0456823A1
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EP
European Patent Office
Prior art keywords
weight
parts
vinyl chloride
chloride resin
tetrahydrofuran
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP90900332A
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German (de)
English (en)
Other versions
EP0456823A4 (en
EP0456823B1 (fr
Inventor
Keisuke Yagi
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Sumitomo Bakelite Co Ltd
Original Assignee
Sumitomo Bakelite Co Ltd
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Application filed by Sumitomo Bakelite Co Ltd filed Critical Sumitomo Bakelite Co Ltd
Publication of EP0456823A1 publication Critical patent/EP0456823A1/fr
Publication of EP0456823A4 publication Critical patent/EP0456823A4/en
Application granted granted Critical
Publication of EP0456823B1 publication Critical patent/EP0456823B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a vinyl chloride resin composition which provides a rubbery elastic material small in temperature dependence of hardness and relates to a tube having heat distortion resistance and high impact resilience and a matte curl cord having high impact resilience which are made by molding the above vinyl chloride resin composition.
  • a vinyl chloride resin is larger than a rubber in temperature dependence of hardness. Therefore, grips and the like which are used outdoor, are apt to change in touch and have severe limitation.
  • temperature-dependent difference of hardness JIS K 6301A type
  • temperature dependence of hardness is small.
  • the dependence shows a high value of about 40 and they are generally inferior in temperature dependence of hardness.
  • Rubbers are mainly employed for uses which require heat distortion resistance and high impact resilience. This is because they possess heat distortion resistance and high impact resilience which are characteristics of rubbers.
  • tubes which use a rubber require vulcanization step and thus suffer from the problems that the number of operation steps increase and besides the material cannot be recycled.
  • non-rigid vinyl chloride resins or thermoplastic elastomer resins are used in some of tubes, but since they are thermoplastic resins, they are low in heat distortion resistance and inferior in creep property and are limited in scope of use.
  • a curl cord coated with a non-rigid vinyl chloride resin composition high in impact resilience which comprises a vinyl chloride resin containing a gel fraction to which a plasticizer is added, is widely used in place of urethane resin and polyester resin.
  • curl cords coated with conventional vinyl chloride resin compositions are inexpensive as compared with urethane and polyester resins and besides show no discoloration and have self-extinguishing properties, they are inferior to urethane or polyester resin-coated curl cords in impact resilience (JIS K6301, which is used also for the measurement referred to hereinafter), heat distortion degree (JIS K6723, which is used also for the measurement referred to hereinafter) and permanent compression set (JIS K6301, 70°C x 22 hr, which is used also for the measurement referred to hereinafter).
  • An object of the present invention is to provide a molded product low in temperature dependence of hardness, specifically, having a temperature dependent-difference of hardness (JIS K 6301A type) of 25 or less in the range of -20°C to 80°C.
  • JIS K 6301A type temperature dependent-difference of hardness
  • Another object of the present invention is to provide a curl cord coated with a vinyl chloride resin composition which is excellent in heat distortion resistances such as heat distortion ratio and permanent compression set, high in impact resilience, superior in processability and has superior matte effect.
  • Another object of the present invention is to provide a tube made by molding a vinyl chloride resin composition which has molding processability similar to that of general thermoplastic resins though it has heat distortion resistance and high impact resilience close to those of rubbers.
  • the present invention is a vinyl chloride resin composition which provides a rubbery elastic material small in temperature dependence of hardness and which is composed mainly of 100 parts by weight of a vinyl chloride resin comprising 8-90% by weight of a tetrahydrofuran-insoluble gel fraction and the remainder of a tetrahydrofuran-soluble fraction, 10-200 parts by weight of a copolyester resin and 25-200 parts by weight of a plasticizer.
  • the present invention provides a tube having heat distortion resistance and high impact resilience which is made by molding the above vinyl chloride resin composition.
  • the present invention provides a matte curl cord of high impact resilience which is characterized by being coated with the above vinyl chloride resin composition which is excellent in heat distortion resistances such as heat distortion ratio and permanent compression set, high in impact resilience, superior in processability and has good matte effect.
  • the characteristic of the vinyl chloride resin composition of the present invention resides in that 10-200 parts by weight, preferably 30-100 parts by weight of a copolyester resin and 25-200 parts by weight, preferably 40-150 parts by weight of a plasticizer are blended with 100 parts by weight of a gel-containing vinyl chloride resin, and this has made it possible to produce molded products low in temperature dependence of hardness. If the copolyester resin is contained in an amount of less than 10 parts by weight, temperature dependence of hardness cannot be improved, and if content of the copolyester resin exceeds 200 parts by weight, the composition sticks much to a kneader and it is not satisfactorily molten.
  • average polymerization degree of the tetrahydrofuran-soluble fraction of the gel-containing vinyl chloride resin With reference to average polymerization degree of the tetrahydrofuran-soluble fraction of the gel-containing vinyl chloride resin, processability is improved with increase in polymerization degree.
  • average polymerization degree of 400-10000, preferably 1800-7000 is employed.
  • Tetrahydrofuran-insoluble gel fraction used in this specification and claims means an extraction residue obtained by subjecting to extraction with hot tetrahydrofuran for 22 hours by a Soxhlet's extractor and separating the extract by a 350 mesh filter.
  • Extrusion molding method is mainly used for obtaining tubes of ordinary shape, but it is also possible to employ injection molding, blow molding or press molding for tubes of short and special shapes.
  • the characteristic of the tube of the present invention resides in that partially crosslinked vinyl chloride resin is blended with a copolyester resin, and thereby it has become possible to produce a tube having heat distortion resistance and high impact resilience by molding methods similar to those used for thermoplastic resins.
  • Amount of the crosslinked portion in the vinyl chloride resin is suitably 8-90% by weight from the points of heat distortion resistance and high impact resilience and processability.
  • Further characteristic of the present invention resides in that there is obtained an impact resilience of about 40-50% which is close to 60-70% of a urethane or polyester resin, by coating a curl cord with a vinyl chloride resin composition composed mainly of 100 parts by weight of a vinyl chloride resin comprising 8-90% by weight of a tetrahydrofuran-insoluble polyvinyl chloride gel fraction and the remainder of a tetrahydrofuran-soluble fraction, 10-200 parts by weight of a copolyester resin and 25-200 parts by weight of a plasticizer.
  • the main component consisting of the vinyl chloride resin of U.S.P. 4,340 ,530, 10-200 parts by weight of a copolyester resin and 25-200 parts by weight of a plasticizer. If any one of them is omitted, impact resilience cannot be close to that of a urethane or polyester resin.
  • a copolyester resin is added to improve the resulting molded product, and addition amount thereof varies depending on use object of the molded product. If amount of a copolyester resin is less than 10 parts by weight, improvement of temperature dependence of hardness cannot be attained, and if it exceeds 200 parts by weight, the composition sticks much to a kneader to deteriorate operability, and many problems occur in processability.
  • the especially preferred range is 30-100 parts by weight and good impact resilience and processability are obtained in this range.
  • copolyester resins examples include those which have PBT (polybutadiene terephthalate) as a hard segment and poly(alkylene oxide) glycol in which the alkylene group has 2-10 carbon atoms, as a soft segment such as poly(ethylene oxide) glycol, poly(1,2- and 1,3- propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(pentamethylene oxide) glycol, poly(hexamethylene oxide) glycol, poly(heptamethylene oxide) glycol, poly(octamethylene oxide) glycol, poly(nonamethylene oxide) glycol, and poly(1,2-butylene oxide) glycol; random or block copolymers of ethylene oxide and 1,2-propylene oxide, and polyformals prepared by reacting formaldehyde with a glycol such as propylene glycol or a glycol mixture such as a mixture of tetramethylene and pentamethylene glycols.
  • PBT polybutadiene terephthalate
  • a plasticizer is added in order to impart rubbery elasticity to the resulting molded product and besides improve impact resilience, and addition amount thereof varies depending on the use object of the molded product.
  • amount of a plasticizer is too small, melting at high temperature and molding under high pressure are required and processing of the resin becomes difficult to result in brittle tubes of poor appearance.
  • a plasticizer is too much, there are various problems in processability and in practical use such as exudation of the plasticizer to the surface of the resulting tube to result in tackiness.
  • amount of a plasticizer is less than 25 parts by weight, impact resilience decreases, and when it is more than 200 parts by weight, productivity and processability deteriorate.
  • the especially preferred range is 40-150 parts by weight in which impact resilience and processability are superior.
  • plasticizers there are cited alkyl esters of aromatic polybasic acids such as dibutyl phthalate, dioctyl phthalate and butylbenzyl phthalate; alkyl esters of aliphatic polybasic acids such as dioctyl adipate, dioctyl azelate and dioctyl sebacate; esters of phosphoric acid such as tricresyl phosphate; and polyesters. There are no differences in impact resilience and processability for all of these plasticizers.
  • polyvinyl chloride resins used in the present invention there may be used those which are used in U.S.P. 4,340,530, and so details thereof are omitted here, but they are characterized by comprising 8-90% by weight of a tetrahydrofuran-insoluble gel fraction and the remainder of a tetrahydrofuran-soluble fraction and include the following copolymers.
  • fatty acid vinyl esters there are cited fatty acid vinyl esters, vinylidene halides, acrylic acid alkyl esters, methacrylic acid alkyl esters, acrylonitrile, alkylvinyl ethers, styrene, ethylene, urethane and derivatives thereof.
  • the vinyl chloride resin composition of the present invention can be utilized as such, but if necessary, may contain another thermoplastic resin, rubber, heat stabilizer, filler, pigment, processing aid, etc.
  • thermoplastic resins include general vinyl chloride resins, ethylene-vinyl acetate copolymer, chlorinated polyethylene, ABS resin, AS resin, urethane, acrylic resins, etc., and NBR, CR and the like are used as a rubber.
  • Heat stabilizers include lead type heat stabilizers such as tribasic lead sulfate; tin type stabilizers such as dibutyltin maleate; and metallic soaps such as zinc stearate, calcium stearate and barium stearate, and addition amount thereof is generally 20 parts by weight or less and can be used as required.
  • fillers there are cited carbon black, calcium carbonate, titanium oxide, talc, asbestos, aluminum hydroxide, magnesium hydroxide, etc. and these can be used as required. Amount thereof is not limited, but they are generally used in an amount of 100 parts by weight or less.
  • Pigments include color carbon black, chrome yellow, titanium oxide, Phthalocyanine Green, etc. and can be used depending on purpose.
  • Processing aids include low-molecular weight polyethylenes, higher fatty acid esters, etc. which are usually used for vinyl chloride resins.
  • the vinyl chloride resin composition of the present invention can be granulated by the same processes as for conventional vinyl chloride resins. That is, the composition is mixed with plasticizer, stabilizer, etc. by a mixer such as super mixer or blender and the mixture is kneaded and granulated by Banbury mixer, mixing roll, extruder, etc. Like general non-rigid vinyl chloride resins, the granulated pellets can be subjected to injection molding, extrusion molding, press molding, blow molding, calender molding, etc. and the processability is superior like non-rigid vinyl chloride resins.
  • the vinyl chloride resin composition comprising a blend of a copolyester resin and a vinyl chloride resin containing a gel fraction according to the present invention can be subjected to granulation by the same process as used for conventional vinyl chloride resins. That is, the composition is mixed with a plasticizer, a stabilizer, etc. by a mixer such as super mixer, blender or the like, and the mixture is kneaded and granulated by Banbury mixer, mixing roll, extruder, or the like.
  • the granulated pellets can be subjected to injection molding, extrusion molding, blow molding, calender molding, and press molding like general non-rigid vinyl chloride resins, and the resulting molded products have good appearance like general non-rigid vinyl chloride resins.
  • the tube of the present invention is superior in processability like tubes made of general vinyl chloride resins and besides has heat distortion resistance and high impact resilience close to those of rubbers. Therefore, the present tube is used as tubes for covering iron wire such as leading tubes and tubes for piping in an engine room of an automobile, protective covering tubes for household appliances and electric wires, and tubes for construction and foods and furthermore, can also be used for transport parts the content of which is liquid, gas or solid.
  • the curl cord of the present invention is superior in processability and heat distortion resistance, has matte effect and is excellent in impact resilience like cords of general vinyl chloride resins.
  • the curl cord is one which is covered with a vinyl chloride type thermoplastic resin which is satisfactory in creep resistance, retention of shape at high temperatures, oil resistance and heat aging resistance which is peculiar to a polyvinyl chloride type resin.
  • a vinyl chloride polymer comprising 20% of a tetrahydrofuran-insoluble gel fraction and the remainder of a tetrahydrofuran-soluble fraction having an average polymerization degree of 5000 (UX-C manufactured by Sumitomo Chemical Co., Ltd.) were added 90 parts by weight of diisononyl phthalate, 3 parts by weight of a barium-zinc type stabilizer (AP-539 manufactured by Adeka Argus Co. Ltd.) and a copolyester resin (HYTREL 4057 manufactured by Toray DuPont Co.) in various amounts. The mixture was kneaded by a Banbury mixer to make pellets.
  • Pressed sheets were produced from the pellets, and temperature-dependent difference of hardness (JIS K6301) of the sheets was measured in the range of -20°C to 80°C, and the results were simultaneously compared with those of NBR, SBR, EPDM and general polyvinyl chloride. Temperature-dependent difference of hardness (JIS K6301) and productivity were evaluated in Table 1.
  • a vinyl chloride polymer comprising 20% of a gel fraction and a tetrahydrofuran-soluble fraction having an average polymerization degree of 5000 (UX-C manufactured by Sumitomo Chemical Co., Ltd.) were added 90 parts by weight of dioctyl phthalate, 3 parts by weight of a barium-zinc type stabilizer (AP-539 manufactured by Adeka Argus Co. Ltd.) and a copolyester resin (HYTREL 4057 manufactured by Toray DuPont Co.) in various amounts. The mixture was kneaded by a Banbury mixer to make pellets. Pressed sheets were prepared from the pellets and were evaluated on heat distortion, impact resilience and operability. The results are shown in Table 2.
  • compositions of Experiment Nos. 1 and 5 used in Example 2 were extruded into molded products having an outer diameter of 12 mm ⁇ and having an iron core of 6 mm ⁇ in the central portion through a cross die of an extruder of 50 mm.
  • the resulting tube-like molded products were cut to a length of 100 mm for examination of heat distortion resistance. They were kept horizontally in an oven of 160°C under application of a load of 1 kg/100 mm for 1 hour and taken out into room temperature, and degree of distortion of the molded products after removal of the load was confirmed. The results are shown in Table 3.
  • a copolyester resin (HYTREL 4057 manufactured by Toray DuPont Co.) was added to a composition composed of 100 parts by weight of a vinyl chloride resin containing 15% by weight of a tetrahydrofuran-insoluble gel fraction and a soluble fraction of 5000 in average polymerization degree which was prepared by the method shown in U.S.P. 4,340,530, 90 parts by weight of diisodecyl phthalate, and 3 parts by weight of a barium-zinc type stabilizer (AP-539 manufactured by Adeka Argus Co.). The mixture was kneaded by a Banbury mixer to prepare pellets. Pressed sheets were prepared from the pellets, and impact resilience and heat distortion rate of them were measured and were evaluated together with productivity. The results are shown in Table 4.
  • a composition composed of 90 parts by weight of diisodecyl phthalate, 3 parts by weight of a barium-zinc type stabilizer (AP-539 manufactured by Adeka Argus Co.) and 60 parts by weight of a copolyester resin (HYTREL 4057 manufactured by Toray DuPont Co. was kneaded by a Banbury mixer to prepare pellets.
  • the vinyl chloride resin composition of the present invention is industrially very useful as molding materials for tubes having heat distortion resistance and high impact resilience and matte curl cords having excellent high impact resilience.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)

Abstract

Résine à base de chlorure de vinyle comprenant en tant que composants principaux 100 parties en poids d'une résine de chlorure de vinyle composée de 8 à 90 % en poids d'un gel insoluble dans le tétrahydrofuranne, le reste étant composé de substances solubles dans le tétrahydrofuranne, 10 à 200 parties en poids d'une résine de copolyester et 25 à 200 parties en poids d'un plastifiant. L'élastomère ainsi obtenu présente une dureté qui ne dépend que faiblement de la température. L'invention se rapporte également à un tube et à un câble spiralé composés de ladite résine.
EP90900332A 1988-06-08 1989-12-07 Resine a base de chlorure de vinyle Expired - Lifetime EP0456823B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP63139382A JPH083965B2 (ja) 1988-06-08 1988-06-08 高反発弾性艶消しカールコード
PCT/JP1989/001227 WO1991009085A1 (fr) 1988-06-08 1989-12-07 Resine a base de chlorure de vinyle

Publications (3)

Publication Number Publication Date
EP0456823A1 true EP0456823A1 (fr) 1991-11-21
EP0456823A4 EP0456823A4 (en) 1992-08-12
EP0456823B1 EP0456823B1 (fr) 1995-12-06

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP90900332A Expired - Lifetime EP0456823B1 (fr) 1988-06-08 1989-12-07 Resine a base de chlorure de vinyle

Country Status (4)

Country Link
EP (1) EP0456823B1 (fr)
JP (1) JPH083965B2 (fr)
DE (1) DE68925036T2 (fr)
WO (1) WO1991009085A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106380719A (zh) * 2016-08-22 2017-02-08 浙江西大门新材料股份有限公司 一种抗菌pvc涤纶包覆丝的制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5438491B2 (ja) * 2009-12-21 2014-03-12 昭和電線ケーブルシステム株式会社 複合フラットケーブル
JP6638630B2 (ja) * 2016-11-30 2020-01-29 株式会社オートネットワーク技術研究所 電線被覆材用組成物および絶縁電線

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2138095A1 (fr) * 1971-05-19 1972-12-29 Du Pont
JPH01311153A (ja) * 1988-06-08 1989-12-15 Sumitomo Bakelite Co Ltd 塩化ビニル系樹脂組成物
EP0390060A1 (fr) * 1989-03-27 1990-10-03 Nippon Zeon Co., Ltd. Composition de résine à fonction mémoire de forme, sa méthode d'utilisation et pièce moulée avec mémoire de forme
JPH06248751A (ja) * 1993-03-02 1994-09-06 Sekisui House Ltd 軒天井構造

Family Cites Families (6)

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Publication number Priority date Publication date Assignee Title
JPS5148169A (en) * 1974-10-22 1976-04-24 Matsushita Electric Ind Co Ltd Kansetsuinsatsu nyoru atsumakukairobuhinno seizohoho
JPS5717325A (en) * 1980-07-02 1982-01-29 Kawasaki Steel Corp Method for cutting long sized steel material
AU594068B2 (en) * 1985-08-08 1990-03-01 B.F. Goodrich Company, The Poly(vinyl chloride)polyblend containing a crystalline polyester with limited miscibility and reinforced composites thereof
JPS6248751A (ja) * 1985-08-28 1987-03-03 Matsushita Electric Ind Co Ltd 耐溶剤性ポリ塩化ビニル組成物とこれを用いた可撓性電線
US4739012A (en) * 1986-02-21 1988-04-19 E. I. Du Pont De Nemours And Company Elastomer blends
JPS62265339A (ja) * 1986-05-14 1987-11-18 Dainippon Ink & Chem Inc 電線被覆用塩化ビニル樹脂組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2138095A1 (fr) * 1971-05-19 1972-12-29 Du Pont
JPH01311153A (ja) * 1988-06-08 1989-12-15 Sumitomo Bakelite Co Ltd 塩化ビニル系樹脂組成物
EP0390060A1 (fr) * 1989-03-27 1990-10-03 Nippon Zeon Co., Ltd. Composition de résine à fonction mémoire de forme, sa méthode d'utilisation et pièce moulée avec mémoire de forme
JPH06248751A (ja) * 1993-03-02 1994-09-06 Sekisui House Ltd 軒天井構造

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF POLYMER SCIENCE, POLYMER CHEMISTRY EDITION. vol. 10, no. 10, 1972, NEW YORK US pages 3111 - 3112; ROGOZINSKY, KRAMER: 'determination of the gel content of vinyl chloride polymers and copolymers' *
See also references of WO9109085A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106380719A (zh) * 2016-08-22 2017-02-08 浙江西大门新材料股份有限公司 一种抗菌pvc涤纶包覆丝的制备方法

Also Published As

Publication number Publication date
WO1991009085A1 (fr) 1991-06-27
JPH083965B2 (ja) 1996-01-17
EP0456823A4 (en) 1992-08-12
JPH01311510A (ja) 1989-12-15
DE68925036D1 (de) 1996-01-18
DE68925036T2 (de) 1996-05-30
EP0456823B1 (fr) 1995-12-06

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